In-situ formation of one-dimensional coordination polymers in molecular junctions

Anton Vladyka, Mickael L. Perrin, Jan Overbeck, Rubén R. Ferradás, Víctor García-Suárez, Markus Gantenbein, Jan Brunner, Marcel Mayor, Jaime Ferrer and Michel Calame

Nature Communications 10, 262 (2019)

DOI: https://doi.org/10.1038/s41467-018-08025-9

We demonstrate the bottom-up in-situ formation of organometallic oligomer chains at the single-molecule level. The chains are formed using the mechanically controllable break
junction technique operated in a liquid environment, and consist of alternating isocyanoterminated benzene monomers coordinated to gold atoms. We show that the chaining process is critically determined by the surface density of molecules. In particular, we demonstrate that by reducing the local supply of molecules within the junction, either by
lowering the molecular concentration or by adding side groups, the oligomerization process can be suppressed. Our experimental results are supported by ab-initio simulations, confirming that the isocyano terminating groups display a high tendency to form molecular chains, as a result of their high affinity for gold. Our findings open the road for the controlled formation of one-dimensional, single coordination-polymer chains as promising model systems of organometallic frameworks.